TWI514093B - Resist layer removing composition and method for removing a resist layer by using such composition - Google Patents

Description

Resist stripper composition and method for stripping the resist using the composition

The present invention relates to a release agent composition in the photolithography step or a residue thereof (hereinafter, the case where these substances are simply referred to as a resist resist) and the use of the composition The method of peeling off the resist of the object. More specifically, it relates to a resist which can be peeled off in the photolithography etching step in the semiconductor field, and further does not adversely affect the tantalum oxide film located under the resist, and can be peeled off. A resist release agent composition of the agent and a peeling method using the resist of the composition.

The photoresist is used in a semiconductor manufacturing process such as an integrated circuit or a transistor, and is used in a photolithography etching step or the like for forming a fine pattern. For example, when a tantalum oxide film is formed on a germanium substrate in a desired pattern, the substrate is processed, for example, in the following procedure. That is, a tantalum oxide film is first formed on the surface of the tantalum substrate, and after the photoresist is coated on the tantalum oxide film, a resist film is formed. Then, exposure and development are performed using a photomask corresponding to the desired pattern, and the desired pattern is obtained. In order to obtain the desired pattern of the substrate, the pattern is used as a mask, and an unnecessary etching film is removed by an etching step such as plasma doping. Finally, by removing the resist and washing the surface of the substrate, a tantalum oxide film having a desired pattern can be obtained.

The method of removing the resist which is not required after the above etching step is mainly known as the following two methods: dry ashing by ashing such as oxygen plasma ashing (for example, a patent) Document 1 and the like, and a wet method such as immersion in a stripping solvent containing various additives. Oxygen plasma ashing, which is an example of dry ashing method, is a method of decomposing, ashing and removing a resist by the reaction of oxygen plasma and a resist, and is a so-called pollution-free method, but removing the resist by ashing. In the case where the end of the reaction is detected incorrectly, the problem that the surface of the substrate is easily damaged or the problem that the remaining surface of the substrate is likely to adhere remains is still present. Also, there must be problems with expensive equipment and the like generally used to generate plasma. Further, regarding the wet type, for example, a strong oxidizing power of peroxosulfuric acid (Caro's acid) obtained by a reaction of hot concentrated sulfuric acid and hydrogen peroxide is known, for example, in the case of an inorganic stripping solvent. A method in which a resist is inorganically liquefied (ashed) and removed (for example, Patent Document 2). However, this method requires the use of concentrated sulfuric acid at a high temperature, which is not only a problem of high risk, but also a hot mixed acid having a strong oxidizing power generates a useless oxide or molten metal on the surface of the metal, so that it is not suitable for, for example, aluminum. The problem of the substrate of the metal wiring such as wiring.

In such a situation, there is a problem that the dry ashing method as described above does not occur, and there is no problem in that the metal wiring of the inorganic stripping solvent represented by the wet type is dissolved, and the like is simple and effective. The method of peeling off the resist is carried out by the method, and it is desirable to have a liquid medicine which satisfies this requirement.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. Hei 5-291129

Patent Document 2: Japanese Patent Laid-Open No. 3-115850

The present invention has been made in view of the above circumstances, and has been proposed to provide a resist stripper composition for a semiconductor substrate and a peeling method using a resist characterized by using the composition, which is simple and easy. Stripping the resist in the photolithography etching step in the semiconductor field, further preventing the germanium oxide film located under the resist agent, the implant layer generated by the plasma doping, the metal wiring applied to the substrate, etc. A resist release agent composition for a semiconductor substrate which can be used as a release resist.

The present invention relates to a resist stripper composition for a semiconductor substrate, which comprises: [I] a carbon radical generator, [II] acid, [III] a reducing agent, and [IV] an organic solvent, and the pH is not reached 7.

Further, the present invention is a method for peeling off a resist, which is characterized by using a semiconductor containing [I] a carbon radical generator, [II] acid, [III] reducing agent, and [IV] organic solvent and having a pH of less than 7 A resist release agent composition for a substrate.

The resist stripper composition of the present invention can easily and easily peel off the resist in the photolithography etching step in the semiconductor field by using [I] a carbon radical generator, [II] acid, [ III] a reducing agent, and an [IV] organic solvent, without adversely affecting the ruthenium oxide film or the implant layer located under the resist, or even the metal wiring applied to the substrate, and the peelable resist.

Further, the peeling method of the resist of the present invention is an effective method for easily and easily peeling off the resist, by using the stripping agent of the above composition, and as described above, it is not located below the resist. A method in which an antimony oxide film or the like is adversely affected and the resist can be easily peeled off.

In other words, the inventors of the present invention have continuously focused on the results of the above-mentioned objects and found that at least the [I] carbon radical generating agent, the [II] acid, the [III] reducing agent, and the [IV] organic substance are produced. The composition of the solvent can be used as a peeling resist. Further, it has been found for the first time that if a composition containing the above components is used, the resist can be peeled off even if a method using a large or expensive device such as plasma ashing is not used. Compared with the conventional impregnation method using peroxosulfuric acid, the resist can be peeled off stably and simply, and the composition can be made into a composition which does not contain a component which dissolves metal, so even for the application of aluminum wiring or the like The substrate of the metal wiring can also be applied to complete the present invention.

Moreover, the present inventors have also found that the carbon radical generating agent in the resist stripper composition of the present invention is less likely to occur in metal wiring than a compound which generates oxygen radicals such as hydrogen peroxide or ozone. Since an oxide film or the like is adversely affected on the surface, the metal wiring such as aluminum wiring is not adversely affected, and the resist can be peeled off.

Further, the present inventors have found that the resist stripper composition of the present invention does not need to contain a compound which generates fluoride ions (fluoride ions) such as hydrogen fluoride or a salt thereof, and is not corroded by hydrogen fluoride or the like. In addition, it has an advantage of being easy to handle and easy to carry out waste liquid treatment, and the like, and is particularly useful as a resist on a semiconductor substrate which is etched by hydrogen fluoride or the like as a tantalum substrate on which an oxide film (tantalum oxide film) is formed. Stripper.

The [I] carbon radical generating agent in the resist stripper composition for a semiconductor substrate of the present invention may, for example, be a compound which appropriately generates a carbon radical by heating or light irradiation, and specifically, for example, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2' - azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 1 An azonitrile-based carbon radical generator such as [(1-cyano-1-methylethyl)azo]carbamamine, for example, 2,2'-azobis{2-methyl-N-[1 ,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamine}, 2,2'-azobis{2-methyl-N-[2-(1-hydroxybutyl)]propanoid Amine}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2'-azobis[N-(2-propenyl)-2 -methylpropionamide], 2,2'-azobis[N-butyl-2-methylpropionamide], 2,2'-azobis[N-cyclohexyl-2-methylpropane Azoguanamine-based carbon radical generator such as guanamine], for example, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis[N-(2) -carboxyl)-2-methylpropionamidine] tetrahydrate and other chain couples A nitrogen-based carbon radical generating agent such as 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis[2-( 2-imidazolin-2-yl)propane]disulfate, 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrate, 2,2'-azobis {2-[1-(2-hydroxyethyl)-2imidazolin-2-yl]propane}dihydrochloride, 2,2'-azobis[2-(2-imidazolin-2-yl) a cyclic azoquinone-based carbon radical generating agent such as propane], 2,2'-azobis(1-imino-1-pyrrolidinyl-2-methylpropane) dihydrochloride, for example, dimethyl An azo ester-based carbon radical generator such as bis-2,2'-azobis(2-methylpropionate), for example, azonitrile such as 4,4'-azobis(4-cyanovaleric acid) A carboxylic acid-based carbon radical generating agent, for example, an azoalkyl-based carbon radical generating agent such as 2,2'-azobis(2,4,4-trimethylpentane), for example, having an azo in a molecule A compound which appropriately generates a carbon radical by heating, such as a macroazo-based carbon radical generator such as a dimethylpolysiloxane compound; for example, benzoin methyl ether, benzene Equivalent ethyl ether, benzoin isopropyl ether, benzoin a benzoin alkyl ether-based carbon radical generator such as butyl ether, for example, diphenylethylenedione ketal such as 2,2-dimethoxy-1,2-diphenylethane-1-one (benzil) Ketal) is a carbon radical generator such as benzophenone, 4,4'-bis(diethylamino)benzophenone, acrylylated benzophenone, benzamidine benzoin Methyl ester, 2-benzylidene naphthalene, 4-benzylidenebiphenyl, 4-benzylidene diphenyl ether, 1,4-diphenylmethylphenyl, [4-(methylbenzene) A benzophenone-based carbon radical generator such as thio)phenyl]phenylmethane, for example, an amine such as p-dimethylamino benzoic acid ethyl ester or p-dimethylamino benzoic acid isoamyl ethyl ester A benzoic acid ester-based carbon radical generator such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropenyl)benzyl]phenyl}-2- A 1,2-hydroxyalkylphenone-based carbon radical generating agent such as methylpropan-1-one or 1-hydroxycyclohexyl phenyl ketone, for example, 2-methyl-1-(4-methylthiophenyl) -2-(N-morpholinyl)propan-1-one, 2-benzyl-2-pyrene Amino-1-(4-(N-morpholinyl)phenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1 a 1,2-aminoalkylphenone-based carbon radical generating agent such as [4-(4-(N-morpholinyl))phenyl]-1-butanone, for example, 2,4,6-trimethyl Benzobenzyl phenylethoxyphosphine oxide, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenyl A mercaptophosphine oxide-based carbon radical generating agent such as phosphine oxide, for example, an onion-based carbon radical generating agent such as ethyl onion, such as chlorothioxanthone, diethyl thiazolone or isopropyl A thioxanthone-based carbon radical generating agent such as thialopone, for example, an acridon-based carbon radical generating agent such as 10-butylchloroacridone, for example, 2,2'-bis(o-chlorobenzene) -4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetra An imidazole-based carbon radical generating agent such as 3,4,5-trimethoxyphenyl)-1,2'-biimidazole, for example, 1,2-octanedione-1-[4-(phenylthio)-2 -(o-benzylidene hydrazide)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(o-B Ester-based carbon a base generator such as bis(η5-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium or the like Titanocene is a compound which generates carbon radicals by light irradiation, such as a carbon radical generator. Further, these carbon radical generating agents may be used singly or in combination of a plurality of them.

Among these [I] carbon radical generating agents, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 2,2'-azobis ( 2,4-Dimethylvaleronitrile), 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylbutyronitrile), 1,1'- An azonitrile-based carbon radical generating agent such as azobis(cyclohexane-1-carbonitrile) or 1-[(1-cyano-1-methylethyl)azo]carbamamine, for example, 2, 2 '-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide}, 2,2'-azobis{2-methyl- N-[2-(1-hydroxybutyl)]propanamine}, 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide], 2,2' - azobis[N-(2-propenyl)-2-methylpropionamide], 2,2'-azobis[N-butyl-2-methylpropanamide], 2,2' -Azoguanamine-based carbon radical generator such as azobis[N-cyclohexyl-2-methylpropionamide], for example, 2,2'-azobis(2-methylpropionamidine) dihydrochloride a chain azo anthraquinone-based carbon radical generator such as 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate, such as dimethyl-2 An azo ester-based carbon radical generator such as 2'-azobis(2-methylpropionate) is appropriately produced by heating. a compound of a radical; for example, a diphenylethylenedione ketal-based carbon radical generator such as 2,2-dimethoxy-1,2-diphenylethane-1-one, such as 2-hydroxy-2- Methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxyl 1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, etc. 1 a 2-hydroxyalkylphenone-based carbon radical generator such as 2-methyl-1-(4-methylthiophenyl)-2-(N-morpholinyl)propan-1-one, 2- Benzyl-2-dimethylamino-1-(4-(N-morpholinyl)phenyl)-butanone-1, 2-(dimethylamino)-2-[(4-A 1,2-Aminoalkylphenone-based carbon radical generator such as phenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. A compound which appropriately emits carbon radicals upon irradiation with light of 750 nm.

Further, among the above-mentioned [I] carbon radical generating agents, among the compounds which generate carbon radicals by heating, there are those which generate carbon radicals even by light irradiation, and correspond to an azonitrile-based carbon radical generating agent. An azo amine-based carbon radical generator, a chain azo-based carbon radical generator, a cyclic azo-based carbon radical generator, an azo ester-based carbon radical generator, etc. Those who generate carbon radicals can generate carbon radicals even when irradiated with light having a wavelength of 200 to 750 nm. In other words, a compound which appropriately generates a carbon radical by heating is usually a carbon radical generated by heating only as described later, but the above-mentioned azonitrile-based carbon radical generator and azoamine-based carbon are free. A compound capable of generating a carbon radical by irradiation with light, such as a base generating agent, a chain azo quinone-based carbon radical generating agent, a cyclic azoquinone-based carbon radical generating agent, or an azo ester-based carbon radical generating agent, The carbon radicals are generated not only by the method of heating but also by the method of irradiating only with light or by heating and light irradiation. Further, a compound which appropriately generates a carbon radical by light irradiation means a person which can easily generate carbon radicals by irradiation with light, and does not mean a person who does not generate carbon radicals by heating. That is, the above-mentioned compound which generates carbon radicals by light irradiation can also generate carbon radicals by heating. As described above, a compound which appropriately generates a carbon radical by irradiation with light is a carbon radical which can be obtained by irradiation with only light, but may be a carbon radical generated by heating alone or by heating and light irradiation. Moreover, the carbon radical generating agent of such a preferable specific example is useful in terms of industrial ease, economy, and efficient peeling of the resist in a short period of time.

Although the action of the [I] carbon radical generating agent of the present invention is not clear, it is presumed that the surface of the resist and the cured film of the resist is decomposed to promote penetration into an organic solvent to be described later, and the resist is promoted. And the like for the solubilization of the solvent.

The [II] acid in the resist stripper composition for a semiconductor substrate of the present invention is not particularly limited as long as it has a function of making the pH of the solution acidic, and specific examples thereof include hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. And other inorganic acids; for example, formic acid, acetic acid, trifluoroacetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, citric acid, citric acid, lauric acid and other aliphatic monocarboxylic acids; for example, oxalic acid, propylene An aliphatic dicarboxylic acid such as acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid or fumaric acid; for example, an aliphatic hydroxycarboxylic acid such as lactic acid, malic acid, tartaric acid or citric acid; for example, aconite An aliphatic tricarboxylic acid such as aconitic acid; an aliphatic ketocarboxylic acid such as pyruvic acid; an aromatic monoacid such as benzoic acid; for example, phthalic acid or different An aromatic dicarboxylic acid such as capric acid or p-citric acid; an aromatic hydroxycarboxylic acid such as salicylic acid or gallic acid; an organic acid such as an aromatic hexacarboxylic acid such as mellitic acid or the like. In addition, the acid of the above-mentioned [II] may be in the form of a salt as long as it exhibits an acidity. Specific examples of the salt include an ammonium salt, an alkali metal salt such as a sodium salt or a potassium salt, and the like. Further, these acids may be used singly or in combination of a plurality of them. Further, in the description, the carboxylic acid having one or more hydroxyl groups in the structure is classified into a hydroxycarboxylic acid regardless of the number of carboxyl groups.

Among these [II] acids, an organic acid is preferred, and it has a property of exhibiting moderate acidity in a solution even when used in a small amount, and is industrially easy to obtain, economical, etc., and is more preferable. It is acetic acid, trifluoroacetic acid, oxalic acid, and citric acid. Inorganic acid is generally supplied as an aqueous solution, and when such a mineral acid is used for a substrate to which a metal wiring is applied, corrosion of the metal wiring is caused by a large amount of water and an acid contained in the inorganic acid. Therefore, when the resist is peeled off for such a substrate, it is preferred not to use a mineral acid. Further, when an alkali metal salt of an inorganic acid or an organic acid is used for the substrate to which the metal wiring is applied, the electrical characteristics on the semiconductor substrate may be deteriorated. Therefore, when the substrate is peeled off, it is preferable not to use the substrate. An alkali metal salt of an inorganic or organic acid.

The action of the [II] acid of the present invention is also unclear, but it is presumed to have a function of promoting the solubilization of the organic solvent by the resist and the resist hardening film.

The [III] reducing agent in the resist stripper composition for a semiconductor substrate of the present invention is not particularly limited as long as it is a compound having a reducing action, and generally, for example, a reducing agent used in the field is used. Specifically, for example, hydrazine or a derivative thereof; for example, a hydroxylamine or a derivative thereof; for example, a sulfite such as sodium sulfite or ammonium sulfite; and a thiosulfuric acid such as sodium thiosulfite or ammonium thiosulfite; a salt; an aldehyde such as formaldehyde or acetaldehyde; a reducing carboxylic acid such as formic acid, oxalic acid, succinic acid, lactic acid, malic acid, citric acid or pyruvic acid; ascorbic acid such as ascorbic acid or ascorbate, isoascorbic acid or erythorbic acid ester A derivative; for example, a five-carbon sugar having a reducing property such as arabinose, xylitol or ribose; and a monosaccharide such as glucose, mannose, fructose or galactose having a reducing hexose or the like. Further, these reducing agents may be used singly or in combination of a plurality of them. Further, among the reducing agents, for example, a carboxylic acid having a reducing property such as formic acid, oxalic acid, succinic acid, lactic acid, malic acid, citric acid or pyruvic acid also exhibits the action as the above-mentioned acid, so that it can be used alone for reduction. The carboxylic acid is used as two constituent components of an acid and a reducing agent.

Among the above derivatives, specific examples of the anthracene derivative include compounds such as hydrazine sulfate and guanidine hydrochloride. Further, specific examples of the hydroxylamine derivative include a hydroxylamine derivative represented by the formula [1] and the like:

(wherein R ¹ represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear or branched carbon number of 1 to 4 having 1 to 3 hydroxyl groups; a substituted alkyl group; R ² represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear chain having 1 to 3 carbon atoms having 1 to 4 carbon atoms Or a branched, substituted alkyl group).

Specific examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms represented by R ¹ and R ² in the above formula [1] include, for example, methyl group, ethyl group, and n-propyl group. Base, isopropyl, n-butyl, isobutyl, t-butyl, tert-butyl, cyclobutyl, n-pentyl, isopentyl, second pentyl, third amyl, neopentyl, 2-methylbutyl, 1,2-dimethylpropyl, 1-ethylpropyl, cyclopentyl, n-hexyl, isohexyl, second hexyl, third hexyl, neohexyl, 2-methylpentyl a group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a 1-ethylbutyl group, a cyclohexyl group, etc., wherein, preferably, an ethyl group, a n-propyl group, an n-butyl group, wherein More preferably ethyl.

Specific examples of the linear or branched substituted alkyl group having 1 to 3 carbon atoms and having 1 to 3 hydroxyl groups represented by R ¹ and R ² in the above general formula [1] include, for example, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, 2,2-dihydroxyethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl 1,2-dihydroxy-n-propyl, 1,3-dihydroxy-n-propyl, 2,2-dihydroxy-n-propyl, 2,3-dihydroxy-n-propyl, 3,3-dihydroxy-n-propyl 1,2,3-trihydroxy-n-propyl, 2,2,3-trihydroxy-n-propyl, 2,3,3-trihydroxy-n-propyl, 1-hydroxyisopropyl, 2-hydroxyisopropyl 1,1-dihydroxyisopropyl, 1,2-dihydroxyisopropyl, 1,3-dihydroxyisopropyl, 1,2,3-trihydroxyisopropyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 1,2-dihydroxy-n-butyl, 1,3-dihydroxy-n-butyl, 1,4-dihydroxy-n-butyl , 2,2-dihydroxy-n-butyl, 2,3-dihydroxy-n-butyl, 2,4-dihydroxy-n-butyl, 3,3-dihydroxy-n-butyl, 3,4-dihydroxy-n-butyl , 4,4-dihydroxy-n-butyl, 1,2,3-trihydroxy-n-butyl, 1,2,4-trihydroxy-n-butyl, 1,3,4- Hydroxy-n-butyl, 2,2,3-trihydroxy-n-butyl, 2,2,4-trihydroxy-n-butyl, 2,3,3-trihydroxy-n-butyl, 3,3,4-trihydroxy-positive Butyl, 2,4,4-trihydroxy-n-butyl, 3,4,4-trihydroxy-n-butyl, 2,3,4-trihydroxy-n-butyl, 1-hydroxy-tert-butyl, 2-hydroxyl Second butyl, 3-hydroxy second butyl, 4-hydroxy second butyl, 1,1-dihydroxy second butyl, 1,2-dihydroxy second butyl, 1,3-dihydroxy Dibutyl, 1,4-dihydroxy second butyl, 2,3-dihydroxy second butyl, 2,4-dihydroxy second butyl, 3,3-dihydroxy second butyl, 3, 4-dihydroxy-tert-butyl, 4,4-dihydroxy-t-butyl, 1-hydroxy-2-methyl-n-propyl, 2-hydroxy-2-methyl-n-propyl, 3-hydroxy-2- Methyl n-propyl, 1,2-dihydroxy-2-methyl-n-propyl, 1,3-dihydroxy-2-methyl-n-propyl, 2,3-dihydroxy-2-methyl-n-propyl , 3,3-dihydroxy-2-methyl-n-propyl, 3-hydroxy-2-hydroxymethyl-n-propyl, 1,2,3-trihydroxy-2-methyl-n-propyl, 1,3, 3-trihydroxy-2-methyl-n-propyl, 2,3,3-trihydroxy-2-methyl-n-propyl, 1,3-dihydroxy-2-hydroxymethyl-n-propyl, 2,3- Dihydroxy-2-hydroxymethyl-n-propyl, 1 -hydroxy-2-methylisopropyl, 1,3-dihydroxy-2-methylisopropyl, 1,3-dihydroxy-2-hydroxymethylisopropyl, etc., of which 2,2 is preferred - Dihydroxyethyl, 2,3-dihydroxy-n-propyl, 3,3-dihydroxy-n-propyl, wherein 2,2-dihydroxyethyl, 2,3-dihydroxy-n-propyl is more preferred.

Specific examples of the above hydroxylamino group-derived derivatives include, for example, compounds used in the field, and specific examples thereof include mono or dimethylhydroxylamine, mono or diethylhydroxylamine, and mono- or di-n-propyl group. Hydroxylamine, mono or diisopropylhydroxylamine, mono or di-n-butylhydroxylamine, mono or diisobutylhydroxylamine, mono or di-tert-butylhydroxylamine, mono or di-tert-butylhydroxylamine, Mono or dicyclobutylhydroxylamine, mono or di-n-pentylhydroxylamine, mono or diisoamylhydroxylamine, mono or di-second amyl hydroxylamine, mono or di-p-pentylhydroxylamine, single or two Neopentyl hydroxylamine, mono or di-2-methylbutylhydroxylamine, mono or bis(1,2-dimethylpropyl)hydroxylamine, mono or di-1-ethylpropylhydroxylamine, single Or dicyclopentylhydroxylamine, mono or di-n-hexylhydroxylamine, mono or diisohexylhydroxylamine, mono or di-second hexylhydroxylamine, mono or di-thylhexylhydroxylamine, mono or di-n-hexylhydroxylamine, Mono or di-2-methylpentylhydroxylamine, mono or bis(1,2-dimethylbutyl)hydroxylamine, mono or bis(2,3-dimethylbutyl)hydroxylamine, single or two 1-ethylbutylhydroxylamine Mono or di(di)alkylhydroxylamine having 1 to 6 carbon atoms such as mono or dicyclohexylhydroxylamine; for example, mono or bis(1-hydroxyethyl)hydroxylamine, mono or bis(2-hydroxyethyl)hydroxyl Amine, mono or bis(1,2-dihydroxyethyl)hydroxylamine, mono or bis(2,2-dihydroxyethyl)hydroxylamine, mono or bis(1-hydroxy-n-propyl)-1-hydroxylamine , mono or bis(2-hydroxy-n-propyl)-1-hydroxylamine, mono or bis(3-hydroxy-n-propyl)-1-hydroxylamine, mono or bis(1,2-dihydroxy-n-propyl)- 1-hydroxyamine, mono or bis(1,3-dihydroxy-n-propyl)-1-hydroxylamine, mono or bis(2,2-dihydroxy-n-propyl)-1-hydroxylamine, single or double (2 , 3-dihydroxy-n-propyl)-1-hydroxylamine, mono or bis(3,3-dihydroxy-n-propyl)-1-hydroxylamine, mono or bis(1,2,3-trihydroxy-n-propyl 1-hydroxyamine, mono or bis(2,2,3-trihydroxy-n-propyl)-1-hydroxylamine, mono or bis(2,3,3-trihydroxy-n-propyl)-1-hydroxylamine , mono or bis(1-hydroxy-n-propyl)-2-hydroxylamine, mono or bis(2-hydroxy-n-propyl)-2-hydroxylamine, mono or bis(1,1-dihydroxy-n-propyl)- 2-hydroxyamine, mono or bis(1,2-dihydroxy-n-propyl)-2-hydroxylamine, mono or bis(1,3-dihydroxy-n-propyl)-2-hydroxylamine, single or double (1,2,3-trihydroxy-n-propyl)-2-hydroxylamine, mono or bis(1-hydroxy-n-butyl)-1-hydroxylamine, mono or bis(2-hydroxy-n-butyl)-1- Hydroxylamine, mono or bis(3-hydroxy-n-butyl)-1-hydroxylamine, mono or bis(4-hydroxy-n-butyl)-1-hydroxylamine, mono or bis(1,2-dihydroxy-n-butyl 1-hydroxyamine, mono or bis(1,3-dihydroxy-n-butyl)-1-hydroxylamine, mono or bis(1,4-dihydroxy-n-butyl)-1-hydroxylamine, single or double (2,2-dihydroxy-n-butyl)-1-hydroxylamine, mono or bis(2,3-dihydroxy-n-butyl)-1-hydroxylamine, mono or bis(2,4-dihydroxy-n-butyl 1-hydroxyamine, mono or bis(3,3-dihydroxy-n-butyl)-1-hydroxylamine, mono or bis(3,4-dihydroxy-n-butyl)-1-hydroxylamine, single or double (4,4-dihydroxy-n-butyl)-1-hydroxylamine, mono or bis(1,2,3-trihydroxy-n-butyl)-1-hydroxylamine, mono- or di-(1,2,4-tri Hydroxy-n-butyl)-1-hydroxylamine, mono or bis(1,3,4-trihydroxy-n-butyl)-1-hydroxylamine, mono or bis(2,2,3-trihydroxy-n-butyl)- 1-hydroxyamine, mono or bis(2,2,4-trihydroxy-n-butyl)-1-hydroxylamine, mono or bis(2,3,3-trihydroxy-n-butyl)-1-hydroxylamine, single Or bis(3,3,4-trihydroxy-n-butyl)-1-hydroxylamine, single Bis(2,4,4-trihydroxy-n-butyl)-1-hydroxylamine, mono or bis(3,4,4-trihydroxy-n-butyl)-1-hydroxylamine, single or double (2,3, 4-trihydroxy-n-butyl)-1-hydroxylamine, mono or bis(1-hydroxy-n-butyl)-2-hydroxylamine, mono or bis(2-hydroxy-n-butyl)-2-hydroxylamine, mono- or Bis(3-hydroxy-n-butyl)-2-hydroxylamine, mono or bis(1-hydroxy-n-butyl)-3-hydroxylamine, mono or bis(1,1-dihydroxy-n-butyl)-2-hydroxyl Amine, mono or bis(1,2-dihydroxy-n-butyl)-2-hydroxylamine, mono or bis(1,3-dihydroxy-n-butyl)-2-hydroxylamine, mono- or di-(1,4- Dihydroxy-n-butyl)-2-hydroxylamine, mono or bis(2,3-dihydroxy-n-butyl)-2-hydroxylamine, mono or bis(2,4-dihydroxy-n-butyl)-2-hydroxyl Amine, mono or bis(1,1-dihydroxy-n-butyl)-3-hydroxylamine, mono or bis(1,2-dihydroxy-n-butyl)-3-hydroxylamine, mono- or di-(2,2- Dihydroxy-n-butyl)-3-hydroxylamine, mono or bis(1-hydroxy-2-methyl-n-propyl)-1-hydroxylamine, mono or bis(2-hydroxy-2-methyl-n-propyl) 1-hydroxyamine, mono or bis(3-hydroxy-2-methyl-n-propyl)-1-hydroxylamine, mono or bis(1,2-dihydroxy-2-methyl-n-propyl)-1- Hydroxylamine, mono or bis(1,3-dihydroxy-2-methyl-propyl 1-hydroxylamine, mono or bis(2,3-dihydroxy-2-methyl-n-propyl)-1-hydroxylamine, mono or bis(3,3-dihydroxy-2-methyl-propyl 1-hydroxylamine, mono or bis(3-hydroxy-2-hydroxymethyl-n-propyl)-1-hydroxylamine, mono or bis(1,2,3-trihydroxy-2-methyl-propanyl 1-hydroxylamine, mono or bis(1,3,3-trihydroxy-2-methyl-n-propyl)-1-hydroxylamine, mono or bis(2,3,3-trihydroxy-2- Methyl-n-propyl)-1-hydroxylamine, mono or bis(1,3-dihydroxy-2-hydroxymethyl-n-propyl)-1-hydroxylamine, mono or bis(2,3-dihydroxy-2 -hydroxymethyl-n-propyl)-1-hydroxylamine, mono or bis(1-hydroxy-2-methyl-n-propyl)-2-hydroxylamine, mono or bis(1,3-dihydroxy-2-methyl Mono- or bis(hydroxyalkyl) having 1 to 4 carbon atoms such as n-propyl)-2-hydroxyamine, mono or bis(1,3-dihydroxy-2-hydroxymethyl-n-propyl)-2-hydroxylamine a hydroxylamine; for example, ethyl hydroxymethylhydroxylamine, ethyl-2-hydroxyethylhydroxylamine, ethyl-1,2-dihydroxyethylhydroxyamine, etc., having a monoalkyl carbon number of 1 to 6 A hydroxylamine derivative such as mono(hydroxyalkyl)hydroxylamine to 4.

The hydroxylamine derivative represented by the above formula [1] can be used commercially, or an epoxy such as glycidol can be added to an aqueous solution of, for example, a hydroxylamine or a monoalkyl-substituted hydroxylamine. After the compound, it is sufficient to suitably synthesize it by a known method such as conducting a reaction at an appropriate temperature.

Specific examples of the above ascorbic acid esters include, for example, ascorbyl stearate, ascorbyl palmitate, ascorbyl dipalmitate, ascorbyl tetrahexyl decanoate, and ascorbyl glucoside. Further, specific examples of the above erythorbic acid ester include compounds such as stearic acid stearic acid ester, isoascorbyl palmitate, isoascorbyl dipalmitate, isoascorbyl tetrahexyl decanoate, and glucosinolate. Among ascorbic acid esters or erythorbic acid esters, for example, sodium ascorbate, sodium ascorbyl sulfate, sodium ascorbyl phosphate, magnesium ascorbyl phosphate, sodium erythorbate, sodium erythorbate, sodium erythorbate, magnesium erythorbate or the like, or an alkali metal or When the alkaline earth metal ascorbate or isoascorbic acid ester is used in a substrate to which a metal wiring is applied, an alkali metal or an alkaline earth metal causes deterioration of electrical characteristics on the metal wiring, and therefore, when the substrate is subjected to peeling of the resist, Ascorbic acid ester or isoascorbic acid ester containing an alkali metal or the like is not used.

Among these [III] reducing agents, from the viewpoints of moderate reduction performance, industrial availability, economy, and the like, it is preferably, for example, a hydroxylamine or a derivative thereof, such as ascorbic acid or ascorbic acid ester, isoascorbic acid or An ascorbic acid derivative such as erythorbic acid ester, more preferably a hydroxylamine derivative, ascorbic acid or ascorbyl ester, wherein most preferably diethylhydroxylamine, bis(2,2-dihydroxyethyl)hydroxylamine, bis ( 2,3-Dihydroxy-n-propyl)-1-hydroxylamine, ascorbic acid, ascorbyl palmitate.

Although the action of the [III] reducing agent of the present invention is not clear, it is presumed that it has a chemical action on the resist and the resist hardening film, and the structure of the (denatured) resist and the resist hardened film is changed. This resist or the like is easy to change the solubilization of the organic solvent.

The [IV] organic solvent in the resist stripper composition for a semiconductor substrate of the present invention is generally, for example, an organic solvent used in the field, and specific examples thereof include methanol, ethanol, n-propanol, and isopropyl alcohol. An alcoholic protic polar organic solvent such as alcohol, n-butanol, tert-butanol, 1-methoxy-2-propanol or ethylene glycol; for example, ethyl acetate, n-propyl acetate, isobutyl acetate, An ester solvent such as ethyl lactate, diethyl oxalate, diethyl tartrate or γ-butyrolactone, for example, a guanamine solvent such as dimethylformamide or N-methylpyrrolidone. For example, an azeotropic solvent such as dimethyl hydrazine or an aprotic polar organic solvent such as a nitrile solvent such as acetonitrile. Among these [IV] organic solvents, isopropanol, ethylene glycol, γ-butyrolactone, and N-methylpyrrolidone which are capable of peeling off the resist in a short time are preferred, and isopropyl alcohol is preferred. Γ-butyrolactone, N-methylpyrrolidone. Further, these organic solvents may be used singly or in combination of a plurality of them. The organic solvent in the resist release agent composition for a semiconductor substrate of the present invention is preferably isopropyl alcohol and γ-butyl. A combination of lactones or a combination of isopropanol and N-methylpyrrolidone.

The action of the [IV] organic solvent of the present invention is to dissolve the resist and the resist hardening film in the organic solvent to dissolve and remove the resist and the resist hardening film.

Further, the resist release agent composition for a semiconductor substrate of the present invention may contain [V] water in addition to the above-described constituent components. By containing water, it contributes to solubilization of a reducing agent or the like which is hardly dissolved in an organic solvent, so that the reducing action of the reducing agent can be smoothly performed, and the resist can be more easily peeled off.

The above-mentioned [V] water system is not particularly limited as long as it does not cause adverse effects in the peeling of the resist, and is, for example, purified water, distilled water, ultrapure water or the like, and among them, ultrapure water is preferable. Since the ultrapure water system contains almost no impurities, it can be suitably used for a substrate to which metal wiring such as aluminum wiring is applied.

Further, the resist stripper composition for a semiconductor substrate of the present invention may contain a [VI] surfactant in addition to the above-described constituent components. By containing a surfactant, solubilization of a reducing agent or the like which is hardly dissolved in an organic solvent is facilitated, and the reducing action of the reducing agent is smoothly exhibited, and the resist can be more easily peeled off.

The above-mentioned [VI] surfactant is not particularly limited as a surfactant which is generally used in the field, and specific examples thereof include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant. Specific examples of the cationic surfactant include a mono-alkylammonium salt such as monostearyl ammonium chloride, distearyl ammonium chloride, and tristearyl ammonium chloride; for example, chlorinated single hard Fatty trimethylammonium chloride, distearyldimethylammonium chloride, stearyl dimethylbenzylammonium chloride, monostearyl bis(polyethoxy)methylammonium chloride, etc. Alkyl ammonium salts; for example, alkylpyridinium salts such as N-whale pyridinium chloride and N-stearylpyridinium chloride; for example, cetylethylmorpholinium ethyl sulfonate, 4-(4,6-dimethoxy-1,3,5-three chloride N,N-dialkylmorpholinium salts such as 2-methyl)-4-methylmorpholinium; for example, fatty acid guanamine salts such as polyethylpolyamine. Further, the anionic surfactant may, for example, be an alkyl carboxylic acid sodium salt, an alkyl carboxylic acid potassium salt, an alkyl carboxylic acid ammonium salt, an alkyl benzene carboxylic acid sodium salt or an alkyl benzene carboxylic acid potassium salt, Ammonium alkylbenzenecarboxylate, polyoxyalkylene alkylcarboxylate sodium salt, polyoxyalkylene alkylcarboxylate carboxylate, polyoxyalkylene alkylcarboxylate ammonium salt, N-oxime Sodium creatinine, potassium N-mercaptocresine, ammonium N-mercapto-sarcosinate, sodium N-mercapto glutamate, potassium N-mercapto glutamate, N-醯An anionic surfactant having a carboxyl group in a molecule such as an ammonium glutamate; for example, an alkyl sulfonate sodium salt, an alkyl sulfonate potassium salt, an alkyl sulfonate ammonium salt, an alkylbenzene sulfonate sodium salt, an alkyl group Potassium benzenesulfonate, ammonium alkylbenzenesulfonate, sodium alkylnaphthalenesulfonate, potassium alkylnaphthalenesulfonate, ammonium alkylnaphthalenesulfonate, sodium polyalkylene alkyl ether sulfonate , polyoxyalkylene alkyl sulfonate potassium salt, polyoxyalkylene alkyl ether sulfonate ammonium salt, N-methyl-N-mercapto taurine sodium salt, N-methyl-N-醯Potassium taurate, N-methyl-N-mercaptouric acid ammonium salt, dialkyl sulfosuccinate sodium salt, dialkyl An anionic surfactant having a sulfonic acid group in a molecule such as potassium acid succinate or ammonium dialkyl sulfosuccinate; for example, sodium alkylphosphonate, potassium alkylphosphonate, alkylphosphonic acid Ammonium salt, sodium alkylphenylphosphonate, potassium alkylphenylphosphonate, ammonium alkylphenylphosphonate, polyoxyalkylene alkylphosphonate sodium salt, polyoxyalkylene alkyl ether ether phosphonic acid An anionic surfactant having a phosphonic acid group in a molecule such as a potassium salt or a polyoxyalkylene alkyl ether phosphonate ammonium salt. Further, the nonionic surfactant may specifically be a polyoxyethylidene ether such as polyoxyethylene ethyl stearyl ether; for example, polyoxyethylidene group such as polyoxyethyl ether Ethers; for example, polyoxyalkylene alkyl phenyl ethers such as polyoxyethylidene phenyl ether; polyoxyalkylene glycols such as polyoxypropyl propylene poly(ethylene glycol); For example, polyoxy-extended ethyl monoalkanoates such as polyoxyethylidene monostearate; for example, polyoxyethylidene amines such as dipolyoxyethyl stearylamine; for example, polyoxyl A dialkyloxyethylamine amine such as ethyl monostearylamine; for example, an alkylamine oxide such as N,N-dimethylalkylamine oxide. Further, the amphoteric surfactant may, for example, be a carboxybetaine such as an alkyl-N,N-dimethylaminoacetate betaine or an alkyl-N,N-dihydroxyethylaminoacetate betaine; For example, a sulfonic acid betaines such as alkyl-N,N-dimethylsulfonylvinylammonium betaine; for example, an imidazole such as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine鎓 鎓 鎓 betaine and the like. Further, these surfactants may be used singly or in combination of a plurality of them.

The resist stripper composition for a semiconductor substrate of the present invention is such that the pH is made less than 7 by containing the [II] acid, and the resist can be peeled off first. Further, even in the pH of the acidic field, a pH in the range of 0 to 4 is preferable, and a pH in the range of 0 to 2 is more preferable. By setting the pH in such a preferred range, the resist can be peeled off in a shorter time and more effectively. Further, the adjustment of the pH is carried out by appropriately adjusting the type or concentration of the above-mentioned acid, and the like, as long as it is set within the above range.

The resist stripper composition for a semiconductor substrate of the present invention contains a [I] carbon radical generator, a [II] acid, a [III] reducing agent, and an [IV] organic solvent, but may further be used in the above components. Contains [V] water. Further, the resist stripper composition for a semiconductor substrate of the present invention is obtained by dissolving the above-described carbon radical generator, acid and reducing agent of the present invention in an organic solvent solution or a mixed solution of an organic solvent and water. It is prepared in an organic solvent solution or a mixed solvent of an organic solvent and water.

In the resist release agent composition for a semiconductor substrate of the present invention, in addition to the constituent components, the weight % concentration of each component in the composition containing water, that is, [I] carbon radical generation, will be further described below. The concentration by weight of the agent, [II] acid, [III] reducing agent, [IV] organic solvent and [V] water.

The weight % concentration of the [I] carbon radical generating agent in the resist stripper composition for a semiconductor substrate of the present invention is such that the weight of the carbon radical generating agent is generally 0.1 to 10 with respect to the total weight of the composition. The weight % is preferably from 0.5 to 10% by weight. If the concentration of the above-mentioned carbon radical generating agent is too low, the carbon radicals required for the peeling of the resist are inevitably reduced, and there is a problem that the resist cannot be sufficiently peeled off.

The weight % concentration of the [II] acid in the resist stripper composition for a semiconductor substrate of the present invention is generally 0.1 to 5% by weight, preferably 0.5 to 5 by weight based on the total weight of the composition. weight%. If the concentration of the above acid used is too low, the pH of the composition becomes too high, and there is a problem that it is difficult to peel off the resist in a short time and effectively.

The weight % concentration of the [III] reducing agent in the resist stripper composition for a semiconductor substrate of the present invention is generally 0.01 to 10% by weight, preferably 0.1, based on the total weight of the composition. Up to 5% by weight. If the use concentration of the above reducing agent is too low, there is a problem that the resist cannot be sufficiently peeled off.

The weight % concentration of the [IV] organic solvent in the resist stripper composition for a semiconductor substrate of the present invention is such that the weight of the organic solvent is generally 60 to 99% by weight, preferably 70, based on the total weight of the composition. Up to 99% by weight. If the concentration of the organic solvent used is too low, there is a problem that the resist cannot be sufficiently peeled off or the resist residue which has been peeled off adheres to the substrate.

The weight % concentration of [V] water in the resist stripper composition for a semiconductor substrate of the present invention is generally 0.01 to 30% by weight, preferably 0.01 to 20% by weight based on the total weight of the composition. weight%. If the concentration of water used is too high, there is a problem that corrosion of metal wiring such as aluminum wiring applied to the substrate occurs. Therefore, when the substrate to be subjected to the peeling of the resist is a substrate to which the metal wiring is applied, the content of water is preferably extremely small.

In the resist stripper composition for a semiconductor substrate of the present invention, as described above, in addition to the [I] carbon radical generating agent, [II] acid, [III] reducing agent, [IV] organic solvent, [ In addition to the V] water and the [VI] surfactant, various auxiliary components may be contained in a range that does not impair the effects of the present invention.

Specific examples of the various auxiliary components are, for example, a metal corrosion preventing agent used for the purpose of protecting metal wiring and preventing corrosion, for example, when a substrate to which metal wiring is applied is used.

Specific examples of the metal corrosion preventing agent include benzotriazole; benzotriazole derivatives such as carboxybenzotriazole and aminobenzotriazole; and thioureas such as thiourea; A thiol compound such as thiazole, mercaptoethanol or thioglycerol; a carboxylic acid derivative such as quinolinecarboxylic acid or the like. Further, these metal corrosion inhibitors can be used singly or in combination of a plurality of them.

The concentration of the auxiliary component to be added to the resist release agent composition for a semiconductor substrate of the present invention is generally as long as it is a concentration range used in the field, specifically, for example, a weight percent concentration of a metal corrosion inhibitor. The weight of the metal corrosion preventing agent is generally from 0.01 to 5% by weight based on the total weight of the composition.

The method for preparing the resist stripper composition for a semiconductor substrate of the present invention may be a method of preparing a solution containing the component of the present invention as described above. Specifically, for example, (1) the [I] carbon radical generating agent, the [II] acid and the [III] reducing agent of the present invention, and the optional [VI] surfactant are directly added to the [IV] organic a method of stirring and dissolving in a solvent; (2) dissolving the [I] carbon radical generating agent, [II] acid, and [III] reducing agent of the present invention, and optionally [VI] a surfactant, respectively, in [IV] a method of mixing the obtained organic solvent solution in an organic solvent; (3) directly adding the [I] carbon radical generating agent of the present invention, [II] in a mixed solvent of [IV] organic solvent and [V] water; Acid and [III] reducing agent, and optionally [VI] surfactant, stirring and dissolving method; (4) in [IV] organic solvent solution in which [I] carbon radical generating agent of the present invention is dissolved A method of adding an [V] aqueous solution in which the [II] acid and [III] reducing agent of the present invention and, if necessary, the [VI] surfactant are dissolved, is added. Among them, the method of (4) is a method of preparing a solution containing an acid at the end, so that it is a preferable preparation method from the viewpoint of easy pH adjustment. Further, since the resist stripper composition for a semiconductor substrate of the present invention contains a carbon radical generating agent, it is preferred to remove a specific region required for the carbon radical generating carbon radical to be generated in a yellow lamp or the like. Modulation is carried out at low temperatures such as illumination under wavelength, under dark, and below room temperature.

Next, in the resist release agent composition for a semiconductor substrate of the present invention, a preferred specific example of the resist to be peeled off and a preferred specific example of the semiconductor substrate will be described.

In the resist release agent composition for a semiconductor substrate of the present invention, the resist film to be peeled off is a resist film formed of a resist material containing an organic polymer compound, and can be used for g-line or i-line. The excimer laser such as KrF or ArF, the electron beam, and the X-ray are not particularly limited. Further, it includes a film which is modified by heat, for example, a film which is surface-hardened by doping with a plasma such as boron or phosphorus. As described above, the resist stripper composition for a semiconductor substrate of the present invention can not only peel off the resist but also peel off the excellent release agent of the resist cured film produced by the plasma doping.

In the resist release agent composition for a semiconductor substrate of the present invention, a specific example of the semiconductor substrate to be used is, for example, a tantalum substrate, a GaAs substrate, a GaP substrate, or the like. Among them, a tantalum substrate is preferable, and further, the tantalum substrate is suitable. A substrate in which an oxide film (an oxide film) is formed on the surface of the substrate. Moreover, the oxide film here is a thermal oxide film, a TEOS oxide film, etc.

In the resist stripper composition for a semiconductor substrate of the present invention, the target semiconductor substrate may be formed by forming at least a resist on the upper surface of the semiconductor substrate such as the tantalum substrate. The substrate is formed on the substrate, and the resist is formed on the substrate above the oxide film. Preferably, the substrate on which the oxide film is formed is a plasma doped substrate.

Further, the semiconductor substrate to be used may be provided with a metal wiring, but it is preferably a semiconductor substrate to which metal wiring is applied, and more preferably a germanium substrate to which metal wiring is applied, and further preferably a metal wiring is applied thereto. Further, a tantalum substrate having an oxide film (tantalum oxide film) is formed. Specific examples of the metal wiring include aluminum wiring, tungsten wiring, copper wiring, aluminum alloy wiring, tungsten alloy wiring, and aluminum-copper alloy wiring. The resist stripper composition for a semiconductor substrate of the present invention can be made into a composition containing only a small amount of water or no water at all, and can also be made to have no adverse effect such as a wiring surface which is fearful of the metal oxide wiring. Since hydrogen peroxide generates a compound (oxygen radical generator) which generates oxygen radicals, it is an excellent stripper which can peel off the resist without corroding the metal wiring even if it is a substrate to which metal wiring is applied. .

As described above, the resist release agent composition for a semiconductor substrate of the present invention is suitably used for a substrate having an oxide film formed on its surface. Therefore, it is preferable that the composition does not substantially contain, for example, hydrogen fluoride or a salt thereof. A compound that dissolves the fluorine source of the ruthenium oxide film, that is, a fluoride ion (fluoride ion). Further, in the resist release agent composition for a semiconductor substrate of the present invention, the operability of the composition can be expected by substantially not containing a compound which causes highly corrosive fluoride ions (fluoride ions). It is easy to change, and the waste liquid treatment becomes easy. In addition, the term "substantially" as used herein refers to the extent that the amount of the ruthenium oxide film or the like which adversely affects the ruthenium oxide film is dissolved, and the amount of impurities is not excessively excluded.

Next, a preferred means for treating the semiconductor substrate on which the resist is formed by using the resist release agent composition for a semiconductor substrate of the present invention and peeling off the resist will be described.

First, in the resist release agent composition for a semiconductor substrate of the present invention, a solution of a composition of the present invention as described above which is prepared in a specific concentration range by the above method is prepared. Then, the peeling of the resist is achieved by appropriately adopting the following method or the like: for example, a method of immersing the semiconductor substrate as described above while irradiating light (active energy ray) of a specific wavelength to the solution; and heating the solution to A method of immersing the semiconductor substrate as described above at a specific temperature, and a method of immersing the semiconductor substrate as described above by the above-described light irradiation and the above-described heating.

The preferred wavelength of light (active energy ray) when irradiating a specific light (active energy ray) is generally a wavelength of 200 to 750 nm, preferably a wavelength of 200 to 450 nm. By irradiating light of such a preferred range of wavelength (active energy ray) to the resist stripper composition for a semiconductor substrate of the present invention, hydrazine is efficiently produced from the carbon radical generating agent of the present invention. The resist can be peeled off in a shorter time and more effectively.

The preferred temperature for heating upon heating to a specific temperature is generally from 30 to 90 ° C, more preferably from 40 to 80 ° C. By heating the resist stripper composition of the semiconductor substrate of the present invention to such a preferred range of temperature, the carbon radical generating agent of the present invention efficiently generates carbon radicals, and can be produced in a shorter time. The resist is peeled off more effectively.

In the resist stripper composition for a semiconductor substrate of the present invention (light-irradiated composition) irradiated with light having a wavelength of the above-mentioned wavelength (active energy ray), it is heated to a specific temperature as described above. The invention relates to a resist stripper composition for a semiconductor substrate [a composition to be heated only] or to a light having a wavelength of the above-mentioned wavelength (active energy ray) and also heated to a specific temperature as described above. In the resist stripper composition for a semiconductor substrate [combined by light irradiation and heating], the preferred immersion time for immersing the semiconductor substrate is 1 to 60 minutes, more preferably 1 to 50 minutes, and most preferably 1 minute. Up to 40 minutes.

In the above method, compared with the method of heating only or the method of combining light irradiation and heating, the method of only irradiating with light is easier to control the formation of carbon radicals of the carbon radical generating agent, and is not easy to be used for the semiconductor substrate. A preferred method that causes adverse effects and is advantageous for cost-effectiveness. Therefore, in the case of peeling off the resist, it is preferred to irradiate the resist stripper composition for a semiconductor substrate of the present invention with light of a preferred wavelength (active energy ray) as described above without heating. Further, when it is necessary to peel the resist in a shorter period of time and efficiently, it is also possible to use a resist release agent composition for a semiconductor substrate of the present invention which is irradiated with light and heated.

Specific examples of the immersion method include a method in which a semiconductor substrate is simply placed in a resist release agent composition for a semiconductor substrate of the present invention during a immersion period; for example, a semiconductor substrate of the present invention is stirred. In the method of immersing the resist release agent composition of the present invention, for example, a method of impregnating a composition of a resist release agent of a semiconductor substrate of the present invention with an inert gas such as nitrogen while immersing the composition; A known immersion method such as a method of immersing a semiconductor substrate while shaking the semiconductor substrate by a method of immersing the semiconductor substrate while moving the semiconductor substrate, such as a conveyor. Any one of the impregnation methods can be employed.

The above-mentioned method for peeling off the resist is basically an example, and other methods may be employed. For example, even in the case of the light irradiation immersion method, the semiconductor substrate may be immersed in the resist release agent composition for a semiconductor substrate of the present invention which is irradiated with light before the immersion without performing light irradiation. method. Further, for example, even in the case of the immersion method of heating, the semiconductor substrate may be immersed in the resist release agent composition for a semiconductor substrate of the present invention which is previously set to a specific temperature before immersion without heating. The method. Further, although the method of peeling off the resist according to the immersion is described here, the resist resist remover composition for a semiconductor substrate of the present invention which is suitably heated or/and irradiated may be applied even if it is not an immersion method. A method of spraying or spraying on a semiconductor substrate or the like. Further, a device required for light irradiation, heating, dipping, stirring, bubbling, coating, spraying, and the like may be used as long as it is generally used in the field.

As described above, the peeling method of the resist of the present invention is an excellent method of peeling off the resist under mild conditions such as light irradiation or heating, without using the plasma ashing performed in the past, and the semiconductor of the present invention. The resist release agent composition for a substrate can be formed into a composition which does not contain a compound which is a fluoride ion (fluoride ion) which is a component which dissolves a ruthenium oxide film or a metal, and is also applicable to the formation of a tantalum oxide film. An excellent method of a germanium substrate or a semiconductor substrate to which metal wiring is applied.

[Examples]

Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these examples. Further, % in the following examples is a weight basis (w/w%) unless otherwise specified.

A substrate having a photoresist film having a thickness of 200 nm is formed on an upper portion of a substrate on which an oxide film is formed on a surface of a wafer having a diameter of 300 mm, and the surface of the resist film is hardened by doping with plasma by boron. A substrate with a resist hardened film. Then, the substrate was cut into 20 mm × 20 mm and thinned to serve as a substrate for evaluation.

Example 1 Preparation of Repellent Release Agent Composition (1) for Semiconductor Substrate of the Present Invention

In the organic solvent solution of 80 g of γ-caprolactone, dimethyl-2,2'-couple was added under irradiation of a yellow lamp (straight tube yellow fluorescent lamp, FLR40SY-IC/M, manufactured by Mitsubishi Electric Osram Co., Ltd.). 1 g of nitrogen bis(2-methylpropionate) (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) was stirred at room temperature. After confirming the dissolution of V-601, the total amount of the aqueous solution obtained by dissolving 0.5 g of ascorbic acid and 3 g of citric acid in 15.5 g of water in advance was added to the solution to prepare a composition (1) of the present invention having a pH of 2. .

Embodiments 2 to 10 Modulation of Repellent Release Agent Compositions (2) to (10) for Semiconductor Substrates of the Present Invention

In each of Examples 2 to 10, the components shown in Table 1 were used, and the compositions of the present invention (2) to (10) were prepared in the same manner as in Example 1 except that the amounts shown in Table 1 were fed. ). The composition of these and the like is shown in Table 1 together with the composition of Example 1. Further, the numerical values shown in Table 1 are the weight % concentrations of the respective components when the total weight of the composition is 100%.

Comparative Example 1 Preparation of Comparative Composition (1)

After 0.5 g of ascorbic acid was added to a mixed solvent of 80 g of γ-butyrolactone and 16.5 g of water, 3 g of citric acid was added to prepare a comparative composition (1) having a pH of 2.

Comparative Examples 2 to 5 Preparation of Comparative Compositions (2) to (5)

In Comparative Example 2, the components shown in Table 2 were used, and the composition for comparison (2) was prepared in the same manner as in Comparative Example 1, except that the amounts shown in Table 2 were fed. Further, in Comparative Examples 3 to 5, the acid of the composition of the present invention was replaced with various bases shown in Table 2, except that the amounts shown in Table 2 were fed, and the same procedure as in Example 1 was carried out, and the preparation was compared. Compositions (3) to (5) were used. The composition of these and the like is shown in Table 2 together with the composition of Comparative Example 1. Further, the numerical values shown in Table 2 are the weight % concentrations of the respective components when the total weight of the composition is 100%.

Example 11 Evaluation of Repellent Release Agent Composition (1) for Semiconductor Substrate of the Present Invention

100 mL of the composition (1) of the present invention prepared in Example 1 was heated to 60 ° C, and the evaluation substrate was immersed for 30 minutes while stirring while maintaining the temperature at 60 °C. Thereafter, it was rinsed with pure water for 30 seconds, and the surface of the substrate was dried with compressed air. After visually observing the dried substrate sample, it was confirmed that the resist was well peeled off. As a result, it was found that when the evaluation substrate was immersed for 30 minutes under stirring in the heated composition of the present invention, not only the resist film but also the resist cured film can be peeled off.

Examples 12 to 19 Evaluation of Repellent Stripper Compositions (2) to (9) for Semiconductor Substrates of the Present Invention

In Examples 12 to 19, the compositions (2) to (9) of the present invention were subjected to the same method as in Example 11 for a specific period of time to visually observe the peeling performance of the resist. The results of these and the results of Example 11 are shown in Table 3.

Example 20 Evaluation of Resist Stripper Composition (10) for Semiconductor Substrate of the Present Invention

100 mL of the composition (10) of the present invention prepared in Example 10, using an ultraviolet irradiation device (UV irradiation device: MUV-35U MUV-PF001 with a filter; manufactured by Moritech Co., Ltd.) at room temperature, while irradiating the center The evaluation substrate was immersed for 20 minutes while stirring at a wavelength of 320 nm (active energy ray). Thereafter, it was rinsed with pure water for 30 seconds, and the surface of the substrate was dried with compressed air. After visually observing the dried substrate sample, it was confirmed that the resist was well peeled off. As a result, it was found that the substrate for evaluation of the present invention was immersed for 20 minutes under stirring while being irradiated with light, whereby not only the resist film but also the resist cured film can be peeled off.

Comparison of Comparative Examples 6 to 10 for Compositions (1) to (5)

In Comparative Examples 6 to 10, the comparative compositions (1) to (5) were immersed for 20 minutes in the same manner as in Example 11. However, in any of the comparative compositions, the resist was hardly peeled off. The results of these are shown in Table 4.

From the results of Examples 11 to 19, it is understood that in the composition in which the carbon radical generating agent contains a compound (thermal radical generating agent) which suitably generates carbon radicals by heating, the resisting agent attached to the cured film can be used. Peeled well. Further, as is apparent from the results of Example 20, a compound (photoradical generator) which suitably generates a carbon radical by means of light is used as a carbon radical generating agent instead of a thermal radical generating agent, and is produced by light irradiation. In the case of a carbon radical, the resist of the cured film can be favorably peeled off.

Further, from the results of Comparative Examples 6 to 10, it is understood that the resist cannot be peeled off without the carbon radical generating agent, and therefore the composition of the present invention contains a carbon radical generating agent as an essential component, and a carbon radical generating agent, The combination of acid, reducing agent, and organic solvent is important. Further, it has been found that a composition in which an alkali is used in place of an acid and the pH is adjusted to be alkaline cannot remove the resist, so that the pH of the solution must be made acidic.

Example 21 Evaluation of Aluminum Dissolution of Aluminum Plate Using Resistive Release Agent Composition (8) for Semiconductor Substrate of the Present Invention

An aluminum plate having a thickness of 0.3 mm and 20 mm × 10 mm was immersed in 5 mL of the composition (8) of the present invention prepared in Example 8 which had been heated to 60 ° C for 20 minutes. After the immersion, the aluminum plate was taken out from the immersion liquid, and the aluminum contained in the immersion liquid was quantified by flameless atomic absorption spectroscopy (AA-280Z, Furnace Atomic Absorption Spectrophotometer; manufactured by Varian Co., Ltd.). Only 0.2 ppm was detected, so that it was found that only 0.2 ppm of aluminum was eluted in the immersion liquid.

Example 22 Evaluation of Tungsten Dissolution of Tungsten Plate Using Resistive Release Agent Composition (8) for Semiconductor Substrate of the Present Invention

In Example 22, the amount of elution of tungsten was confirmed by the same method as in Example 21 except that the metal plate to be evaluated was changed from an aluminum plate to a tungsten plate. As a result, since only 0.5 ppm was detected, it was found that only 0.5 ppm of tungsten was eluted in the immersion liquid.

Comparative Examples 11 to 12 Metal Dissolution Evaluation of Metal Plates Using Peroxosulfuric Acid (Caroic Acid)

In Comparative Examples 11 to 12, peracetic acid (caroic acid) 5 mL prepared by mixing 98% sulfuric acid and 35% hydrogen peroxide water at a ratio of 10:1 in terms of weight ratio and heating to 130 ° C was used. In Comparative Example 11, the metal plate to be evaluated was an aluminum plate, and the tungsten plate was used in Comparative Example 12, except that the aluminum and tungsten were confirmed in the same manner as in Example 21. The amount of dissolution. As a result, 3 ppm of aluminum was detected in Comparative Example 11, and 1 ppm of tungsten was detected in Comparative Example 12. From this result, it was found that 3 ppm of aluminum was eluted in the immersion liquid, and 1 ppm of tungsten was eluted. Further, the results of Examples 21 to 22 and Comparative Examples 11 to 12 are shown in Table 5.

From the results of the examples 21 to 22 and the comparative examples 11 to 12, it is understood that the resist release agent composition for a semiconductor substrate of the present invention is difficult to dissolve a metal plate such as an aluminum plate or a tungsten plate, so that a metal such as aluminum or tungsten has been applied. In the wiring substrate, even if the resist stripper composition for a semiconductor substrate of the present invention is used, it is less likely to cause adverse effects such as dissolution of such metal wiring. In addition, pervaporic acid (caroic acid) which is a conventionally known resist release agent tends to dissolve a metal plate such as an aluminum plate or a tungsten plate, and is therefore used when a semiconductor substrate having metal wiring such as aluminum or tungsten is applied. There is a possibility that the metal wiring is broken or the like.

From the above results, it is understood that when the semiconductor substrate on which the resist is formed is treated by using the resist release agent composition for a semiconductor substrate of the present invention, the resist can be efficiently peeled off by a simple method such as dipping, even if it is used. A semiconductor substrate provided with metal wiring such as aluminum wiring does not adversely affect such metal wiring, and it is expected to efficiently strip the resist.

(industrial availability)

The resist stripper composition for a semiconductor substrate of the present invention can easily and efficiently strip the resist in the photolithography etching step in the semiconductor field, and further, the resist cured film which is formed when the plasma is doped Stripped. Further, since the metal strip for the semiconductor substrate is not adversely affected, the resist stripper composition for a semiconductor substrate of the present invention can be expected to be suitably used for a semiconductor substrate to which a metal wiring has been applied. Further, since a composition which does not contain a compound which generates, for example, a fluorine ion (fluoride ion) such as highly corrosive hydrogen fluoride or a salt thereof, the resist release agent composition for a semiconductor substrate of the present invention is not only easy. It is also easy to handle the waste liquid, and it is also expected to be a substrate suitable for forming an oxide film (an oxide film) which may be corroded by hydrogen fluoride or the like.

Further, since the peeling method of the resist of the present invention is a method in which the resist can be easily and efficiently peeled off under mild conditions, it is necessary to handle a large and expensive apparatus, or even if it is not used in the conventional ashing or the like. It is possible to peel off the metal wiring without causing adverse effects such as dissolution of metal wiring or surface oxidation by using a hot mixed acid such as a caroic acid, or to peel off the resist.

Claims (15)

A resist stripper composition for a semiconductor substrate, comprising: a [I] carbon radical generator, a [II] acid, a [III] reducing agent, and an [IV] organic solvent, and having a pH of less than 7, the aforementioned [1] The weight % of the carbon radical generating agent is 0.1 to 10% by weight, the weight % of the aforementioned [II] acid is 0.1 to 5% by weight, and the weight % of the aforementioned [III] reducing agent is 0.01 to 10% by weight, the aforementioned [IV] The weight % of the organic solvent is from 60 to 99% by weight. The composition according to claim 1, wherein the [V] water is further contained, and the weight % of the [V] water is 0.01 to 30% by weight. The composition of claim 2, wherein the [VI] surfactant is further contained. The composition according to claim 1, wherein the [I] carbon radical generating agent is a compound which generates a carbon radical by irradiation with light having a wavelength of 200 to 750 nm. The composition according to claim 1, wherein the [II] acid is an organic acid. The composition according to claim 1, wherein the [II] acid is at least one selected from the group consisting of acetic acid, trifluoroacetic acid, oxalic acid, and citric acid. The composition according to claim 1, wherein the reducing agent (III) is at least one selected from the group consisting of a hydroxylamine derivative, ascorbic acid and ascorbic acid ester. The composition of claim 1, wherein the pH is in the range of 0 to 4. The composition according to claim 1, wherein the semiconductor substrate is a tantalum substrate on which an oxide film is formed. The composition according to claim 1, wherein the semiconductor substrate is a germanium substrate on which an oxide film is formed, and a resist is formed on the upper portion of the oxide film. The composition according to claim 9, wherein the ruthenium substrate on which the oxide film is formed is plasma doping. The composition according to claim 9, wherein the substrate on which the oxide film is formed is a metal wiring. The composition according to claim 12, wherein the metal wiring is an aluminum wiring, a tungsten wiring, or a copper wiring. The composition according to claim 1, wherein the compound which produces fluorine ions is substantially not contained. A method for peeling off a resist, comprising: the steps of (1) and (2) below; (1) irradiating light (active energy ray) or/and a composition according to claim 1 of the patent application scope a step of heating; (2) a step of stripping the resist on the semiconductor substrate with the irradiated light (active energy ray) or/and the heated composition.